JPH05507962A - Post-expanded anionic acrylic dispersion - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Post-expanded anionic acrylic dispersion field of invention The present invention provides a water-based anionic acrylic composition for use as a base coat for multilayer automotive coatings. Regarding the dispersion, more specifically, after-treatment with a compound containing at least two oxirane groups, of anionic acrylic dispersion.

Background of the invention Multilayer coating systems have been developed to improve the aesthetic appearance of coated substrates. “Baseco A relatively thin colored layer called a clear coat is applied, followed by a clear coat. By applying a thicker, unpigmented layer, a "wet look" is generally achieved. It is possible to achieve a glossy coating with a deep appearance.

Multilayer systems have been used extensively in automotive painting for many years.

This system initially used organic solvents, but as environmental regulations became more stringent, Systems containing organic solvents have become less desirable. Multi-layer systems, especially base coat systems Recent research in the field has focused attention on the development of water-based paint systems for multilayer coatings. ing.

In particular, what is called "high solids" painting in this industry uses as little organic solvent as possible. As organic solvent-based paints are formulated, the appearance, especially of coatings containing flake pigments, is changing. It has become clear that the talic effect is adversely affected by an increase in solids content.

One of the benefits of water-based paint systems is the regulation of volatile organic components (VOCs). The objective is to improve the metallic effect in paints that comply with regulations.

However, other problems arose with water-based paint systems.

In the past, sag protection, proper edge coating, and metallics used in paints Rheological tuning to provide desirable application properties such as proper orientation of the flakes. I rely on medication. There are only a limited number of rheology modifiers suitable for water-based automotive paints. ing. In many cases, available rheology modifiers are difficult to disperse or has poor stability. Among the rheology modifiers effectively used in organic paints: Backhaus invention, microgeme in U.S. Pat. No. 4,403,003. Some are used in water-based paints, such as Ru. However, these microgames However, the disadvantages of this method are that it is difficult to manufacture and difficult to stabilize.

U.S. Pat. No. 4,880,867 describes acrylic dispersions and polyurethane dispersions. Discloses an aqueous coating composition that can be applied by electrostatic spraying and comprises a mixture of Ru.

However, acrylic polymers are produced by solution polymerization at high molecular weights prior to dispersion. suitable A large amount of solvent is required to carry out solution polymerization at a viscosity of 100%. Obtain low VoC coating requires distillative separation of organic solvent in excess of that required for a stable dispersion. be. It also acts as a rheology modifier to obtain the desired appearance of the film. It is necessary to add a commercially available thickener.

Moreover, in multilayer coating systems, the base coat is resistant to It is necessary to have J-character. "Interruption" resistance refers to the strength of the base coat and top coat. means the ability to withstand attack by solvents in a composition. Automakers are Topcoat compositions are commonly used in pigmented and transparent systems for ``wet-on-wet'' coatings. This interruption is a problem because you want to apply it by technique. In other words, the base After applying a base coat composition on the material, followed by a top coat composition, A single bake hardens the composite coating in the process. To the top coat base coat "Interruptions" are particularly undesirable because they have a negative effect on the orientation of metallic pigments. . In highly pigmented paints, particles of non-metallic pigments are used to prevent breakouts. can form a physical barrier. However, silver and light metallic In dark colors, there is not enough pigment to prevent cut-in. Prevent this interrupt requires the use of flow modifiers or filler pigments.

The anionic acrylic dispersion that has been increased in weight after the present invention can be It can satisfy logic adjustment and interrupt resistance. In particular, this dispersion Excellent metallic film in basecoat or one-coat topcoat compositions. A rake orientation is obtained. Moreover, this dispersion overcomes the dispersion difficulties found in other compositions. stability, instability, presence of harmful emulsion polymerization surfactants, and high volatility Questions regarding the organic content and the complex production methods of sterically stabilized dispersions. Overcoming the problem.

The purpose of the present invention is to provide excellent rheology control properties and to provide a base coat with flake pigments. Water-based acrylics in base coats for automotive paint systems to improve metallic appearance Another object of the present invention is to provide a dispersion. Another object of the present invention is to An object of the present invention is to provide a base coat containing a dispersion. Yet another object of the present invention is to To provide a method for applying a substrate comprising a krylic dispersion and a substrate coated with the same. That is.

Summary of the invention The purpose of the present invention is to a) selected from the group consisting of carboxylic acid groups, carboxylic anhydride groups or mixtures thereof; Dispersing an acrylic resin with a functional group in water in the presence of a tertiary amine and, and b) The carboxylic acid group of the acrylic resin has at least two oxirane groups. achieved by an aqueous acrylic dispersion obtained by reacting with an organic compound. Ru.

Detailed description of the invention Suitable acrylic resins of the present invention include: f) about 1 to 30 ethylenically unsaturated carboxylic acids or anhydrides or mixtures thereof; weight%, 11) about 20-90% by weight of other ethylenically unsaturated monomers, 111) increased after Ethylenically unsaturated monomers with functional groups that can be crosslinked after formation of an acrylic dispersion Approximately 0-50% by weight Consisting of

Preferred acrylic resins are 1) about 1 to 20 ethylenically unsaturated carboxylic acids or anhydrides or mixtures thereof weight%, if) about 40-85% by weight of other ethylenically unsaturated monomers, 111) increased after Ethylenically unsaturated monomers with functional sites that can be crosslinked after formation of an acrylic dispersion -2 to 40% by weight Consisting of

The most preferred acrylic resin is 1) about 3 to 15 ethylenically unsaturated carboxylic acids or anhydrides or mixtures thereof weight%, 1i) about 55-85% by weight of other ethylenically unsaturated monomers, increased after Ethylenically unsaturated monomers with functional sites that can be crosslinked after formation of an acrylic dispersion -5 to 30% by weight Consisting of

The preferred ethylenically unsaturated carboxylic acid or carboxylic acid anhydride monomer (i) is , acrylic acid, methacrylic acid, acrylicoxypropionic acid or polyacrylic acid Acid mixtures, methacrylic acid dimer or polymethacrylic acid mixtures, crotonic acid, Malic acid, maleic acid or maleic anhydride, itaconic acid or itaconic anhydride and monoalkyl esters of maleic, itaconic or fumaric acids. Ru.

The other ethylenically unsaturated monomer (ii) is an atom having from 1 to about 20 carbon atoms. Acrylic acid or methacrylic acid alkyl esters derived from alcohol, or vinyl monomers. (Meta) actuator with 0 used here The expression lyric acid ester includes methacrylic acid ester and acrylic acid ester . Suitable examples include methyl (meth)acrylate, ethyl (meth)acrylate, Propyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate Isobutyl acetate, (meth)acrylic acid tert, -butyl and (meth)acrylate ) 2-ethylhexyl acrylate, the alkyl group having 1 to 20 carbon atoms Dialkyl esters of maleic or fumaric acid, styrene, alpha-methyl Vinyl aromatization such as styrene, vinyltoluene, tert-butylstyrene compounds, halogenated vinylbenzenes such as chlorostyrene, vinyl chloride, (meth) There are other monomers such as acrylamide and (meth)acrylonitrile.

Ethylenically unsaturated with crosslinkable functional groups after the formation of a post-scaled acrylic dispersion. Examples of Japanese monomers (fil) include hydroxyethyl acrylate, methacryl Hydroxyethyl acid, Hydroxypropyl acrylate, Hydroxy methacrylate Propyl, ethyl isocyanate methacrylate, hydroxybutyl acrylate, Hydroxybutyl methacrylate, propylene glycol monoacrylate, methacrylate 2,3-dihydroxypropyl lylate, pentaerythritol monomethacrylate , propylene glycol monoacrylic acid and monomethacrylate, and meth- Isopropyl-α,α-dimethylbenzyl isocyanate, monoacrylic acid poly Ethylene glycol, polyethylene glycol monomethacrylate and glycerin There is Ruaryl Ether.

Other examples of (ili) include 2 to 20 straight chain, branched or cyclic alkyl groups; dihydroxyalkyl esters of maleic and fumaric acids with carbon atoms of There is a le.

N-hydroxyalkyl (meth)acrylamide and N-hydroxyalkyl Fumaric acid mono- or diamide, such as N-hydroxyethylacrylamide or N-(2-hydroxypropyl) methacrylamide can also be used. other hydroxyl groups Containing compounds include allyl alcohol, polyols, and especially monovinyl esters of diols. ethers, such as monovinyl ethers of ethylene glycol and butanediol , and hydroxyl group-containing allyl ethers or esters, such as 2,3-dihydroxy Cypropyl monoallyl ether, trimethylolpropane monoallyl ether or or allyl ester of 2,3-dihydroxypropanoic acid.

Copolymerization is carried out by conventional methods, for example by adding a polymerization initiator and optionally a chain transfer agent. This is done by heating the monomers in the presence of Copolymerization can be carried out in bulk or in solution. It can be done with In the present invention, there is a solvent that acts as a co-solvent during dispersion. It is preferable that it exists to some degree. Suitable solvents for solution polymerization are ethylene glycol or is propylene glycol and its derivatives, e.g. dipropylene glycol monomethyl ether and ethylene glycol monobutyl ether acetate, Alcohols such as butyl alcohol and diacetone alcohol, ketones, e.g. For example methyl propyl ketone and acetone, esters such as butyl acetate and Pentyl propionate, ethers such as dioxane and tetrahydrofuran , and other compatible solvents such as water and N-methylpyrrolidone, and It is a mixture of them. One of the preferred mixtures is ethylene glycol monobutyl They are ether and water.

Typical initiators are peroxides such as dialkyl peroxides, peroxy esters, Peroxydicarbonates, diacyl peroxides, hydroperoxides, and peroxides Oxyketals and azo compounds, such as 2,2′-azobis(2-methylbutylene) cyclohexanecarbonitrile) and 1.1″-azobis(cyclohexanecarbonitrile). Ru.

Typical chain transfer agents are octyl mercaptan, n- or tert, - Mercaptans such as dodecyl mercaptan, halogen compounds, thiosalicylic acid, Mercaptoacetic acid, mercaptoethanol, buten-1-ol, and dimer amines It is rufer methyl styrene. Mercaptans are preferred.

The reaction is usually carried out at a temperature of about 20 to about 200°C. Temperature below reflux by proper adjustment It is convenient to carry out the reaction at the reflux temperature of the solvent. Initiator reacts is compatible with the temperature at which the initiator is carried out, and the half-life of the initiator at that temperature is preferably Choose between 1 minute and 30 minutes.

The solvent or solvent mixture is typically heated to reaction temperature to remove the monomers and initiator. Add at a controlled rate, usually between 2 and 6 hours. During this time, the chain transfer agent or Additional solvent can also be added at a controlled rate.

The temperature of the mixture is then maintained for a certain period of time to complete the reaction. If desired, further An initiator can be added to ensure conversion.

The acid value of the acrylic resin is about 1 to about 230 gK OH/g, preferably about 7 to about 1 56 mgKOH/g, most preferably about 23 to about 117 mgKOH/g.

The weight average molecular weight of the acrylic resin as measured by GPC versus polystyrene standards is approximately 4 ,000 to about 40,000, preferably about 10,000 to about 25,000 . The theoretical Tg of the acrylic resin is about -30°C to about 150°C, preferably about -30°C to about 150°C. The temperature is 50°C. The theory Tg is based on Bul 1. by Fox. Amer, Phys. tcsSoc, s Volume 1, No. 2.123 (1956) It can be measured as follows.

Acrylic resins are treated with tertiary amines or amino alcohols before being dispersed in water. to at least partially neutralize it. Suitable tertiary amines include, for example, trimethylamine. Triethylamine, dimethylaniline, diethylaniline and N-methylene lumorpholine and N-ethylmorpholine. The preferred amino alcohol is dimethylethanolamine and triethanolamine. After neutralizing Dilute the acrylic resin with deionized water while stirring to obtain a fine particle dispersion.

An organic compound having at least two oxirane groups is added to this acrylic dispersion. I can do it. Suitable compounds include diols, triols and bisphenol di- and It is a derivative of triglycidyl ether or cyclohexene oxide. as an example These include 1,4-butanediol, neopentyl glycol, and cyclohexane dimethane. Tatool, diethylene glycol, polyethylene glycol, dipropylene glycol Cole, polypropylene glycol, 2.2.4-trimethyl-1,3-benta 1,6-hexanediol, bisphenol A and resorcinol trimethylolpropane, trimethylolpropane, trimethylolpropane, trimethylolpropane, There are triglycidyl ethers of tan and glycerin.

Preferred derivatives of cyclohexene oxide have 2 or 3 epoxy groups, For example, in October 1989, Union Carbide Kei, which is included here for reference. Published by Michals & Plastics Technology Corporation It is described in the pamphlet “Cycloaliphatic Epoxide Systems”. listed there The compounds are ERL-4221, ERL-4299, and ERL-4234. . UCC is the trade name of ERLX-4359, has a molecular weight of 406.46, and has a molecular weight of 406.46. Another cyclohexene oxide derivative is described which is a poxide.

Preferred compounds are 1,4-butanediol, cyclohexane dimetatool, poly Lipropylene glycol and diglycidyl ether of bisphenol A, and triglycidyl ether of trimethylolpropane and cyclohexene. It is a derivative of oxide.

The molar ratio of carboxyl groups to epoxide groups is about 20=1 to about 1=1, preferably and about 8=1 to about 1.3:1.

The reaction between the carboxylic acid group and the oxirane group takes from about 30% to about 100% of theoretical completion. %, preferably from about 50% to about 100%, most preferably from about 60% to about 100%. It will be done.

The reaction temperature is not particularly important, but in order for the reaction to proceed in an economical time, approximately 8 0 to about 100°C is preferred.

The above aqueous acrylic dispersion contains a ground resin, a crosslinker, a pigment, aluminum and/or Or flake pigments such as mica particles, basifying agents, water, fillers, surfactants. , stabilizers, plasticizers, wetting agents, dispersants, adhesion promoters, defoamers, catalysts and optionally waterborne base coating, along with additional polymers or rheology modifiers, and other raw materials. It can be added to the

Generally, aqueous acrylic dispersions formulated as described herein contain crosslinkers, water, , some organic solvents, aluminum and/or mica particles, or ground resin. Mix with other pigments that can be used and dispersed.

This aqueous acrylic dispersion can be used as the main resin.

Additionally, these dispersions can be used together with other aqueous resin dispersions that are the main resins. Can also be done. Generally, this aqueous acrylic dispersion is present in the basecoat composition. It comprises from about 10 to about 80% by weight of the total solids present.

A compound that acts as a crosslinking agent has two or more functional groups that can react with functional groups on the resin. has. Crosslinkers may be monomeric or polymeric.

For example, crosslinkers can be acrylic, polyester, alkyd, epoxy or amino Can be blasted resin or blocked polyisocyanate or mixtures thereof . Aminoblast resin is an aldehyde condensation of melamine, urea and similar compounds It is a product. Reaction between formaldehyde and melamine, urea or benzoguanamine The products obtained from the reaction are the most common and preferred for the present invention. However, other amines and condensation products of amides, such as triazines, diazines, triazoles, guar Nidine, guanamine, and alkyl and aryl substituted ureas and alkyl Aldehyde condensates of melamine and aryl substituted melamines can also be used. . Examples of such compounds include N,N-dimethylurea, benzourea, dicyanide. diamide, formguanamine, acetoguanamine, amerine, 2-chloro-4, 6-diamino-1, 3,5-triazine, 6-methyl-2,4-diamino-1, 3,5-triazine, 3,5-diamino-triazole, triaminopyrimidine , 2-mercapto-4,6-diamitupyrimidine, 2,4.6-dryethyltri Amino-1,3,5-triazine, etc.

The aldehyde used is most often formaldehyde, but other aldehydes such as acetaldehyde, crotonaldehyde, acrolein, benzal Similar condensation products can also be prepared from dehydes, furfural, and others.

Amine-aldehyde condensation products contain methylol or similar alkylol groups. , in most cases at least some of these alkylol groups are combined with alcohols. The reaction is etherified to give a resin soluble in organic solvents.

For this purpose, methanol, ethanol, propatool, butanol, pentanoyl alcohol, hexanol, heptatool, and others, as well as benzyl alcohol and and other aromatic alcohols, cyclic alcohols such as cyclohexanol, glyco monoethers of polymers, such as Cellosolve and Calpitol™ (Union Cal). ), and halogen-substituted or other substituted alcohols, e.g. All monohydric alcohols can be used, including 3-chloropropanol. Ru. Preferred amine-aldehyde resins are etherified with methanol or butanol. be converted into

Pigments are ground using a suitable grinding resin by known methods of producing pigment grinding pastes. can be incorporated into the base coat.

Examples of dyes or pigments may be inorganic or organic, such as graphite. , carbon black, zinc chromate, strontium chromate, barium chromate aluminum, lead chromate, cyanide, titanium dioxide, zinc oxide, iron oxide, cadmium sulfide aluminum flakes, mica flakes, zinc sulfide, phthalocyanine complex salts, Naphthol red, carbazole violet, perylene red, quinacridone and halogenated thioindigo pigments, among others.

Preferred flake pigments are aluminum metal flakes and mica. Like New mica is manufactured by Marl Corporation, New York, NY, and EM Chem. Available from Calus, Hawthorne, NY. Preferred aluminum flake pigment is Silverline Corporation, Pennsylvania, or Ecarte V. Available from Elke, Gunterstahl, Germany. Preferred implementation of the invention Form uses standard grade aluminum stabilized with phosphate esters . Flake pigments can also be mixed with non-flake pigments, but these pigments Careful selection is required so as not to impair the desired metallic effect.

The resin used in the base coat is dispersed in deionized water. Deionized water is The conductivity reading is 1 to prevent foaming caused by the reaction between aluminum and water. Preferably it is less than 3 micro ohms. Also normally present in tap water Also choose deionized water to avoid salts. Other solvents can also be used with deionized water. Ru. Particularly preferred solvents facilitate mixing, formulation and dispersion of pigments into base coats. It is ethylene glycol monobutyl ether (Butyl Cellosolve™).

Other solvents, such as low-boiling mono- and polyhydric alcohols, ethers, esters, ketones. Tons and other organic solvents can also be used. Base coat maximum approximately 80% including water %, preferably about 10-20% by weight of the organic solvent in the final base coat. selected in order to improve the dispersibility of the individual components of the can be done.

The final base coat exhibits excellent rheology control.

However, rheology modifiers can also be incorporated into the base coat if desired. . Rheology modifiers that can be used in embodiments of the invention include fumed silica compounds. and bentonite clay. Preferred dry silica compounds include hydrophobic silica compounds. lyca compounds, such as the commercially available A. There is Rosil R972. Others available and preferred in certain base coats The rheology modifier is a synthetic sodium lithium magnesium silicate hectra It's Itokray.

Examples of such companies include Laporte, Industries, Saddle Plutsuk. There is Labonite RD commercially available from , NJ. In some preferred embodiments mix rheology modifier. If rheology modifiers are included, the best from about 0.1 to about 20%, preferably from about 1 to about 5% by weight of the final basecoat composition Use in the amount of

The final base coat is coated with a tertiary amine such as N-ethylmorpholine at pH 7.6. Adjust to ~7.8. Viscosity can be adjusted using deionized water.

The solids content of the final aqueous basecoat is from about 10 to about 60% by weight, preferably about 15 to about 45% by weight.

The coated substrate of the present invention includes at least one coating layer in close contact with the substrate. in general, The substrate to be coated may be metal, plastic, wood, ceramic, etc. Preferably The substrate is metal or plastic, most preferably the substrate is an automobile body. Ru. The substrate is preferably "pre-coated" (i.e. formulated with the acrylic compound of the invention). coat with primer or other desired paint) and then The coating formulation of the present invention is applied to.

The base coat described above is applied to the prepared metal or plastic substrate, e.g. Sprayer (Binks Model 60 Spray Gun, Pinks Manufacturer) (commercially available from NG Corporation, Franklin Burke, IL). Can be applied in one or two coats using spray or other conventional spraying methods. I can do it.

This base coat can also be applied electrostatically.

After application, the base coat is heated to a relative humidity of about 5 to about 40% using a hot air blower. Dry at a temperature of room temperature to about 145@F for about 30 seconds to about 10 minutes. Preferably , about 120"F for about 1 to about 5 minutes. Under the drying conditions described herein, about 90 to about 95% of the water-containing solvent is removed from the base coat within a short period of time.

After depositing the first base coat, without drying (evaporation separation), apply the second base coat. The coat can be deposited over the first base coat or allowed to dry. A clear coat can be deposited over the base coat.

Any clear coat known in the art can be used. With clear coat Any unpigmented or clear-pigmented paint may be used. Wear. A typical rear coat composition contains about 30% to about 70% film-forming resin or and about 30 to about 70% volatile organic solvent.

After applying the clear coat over the base coat, the multilayer coating is baked to cross-link. to remove small amounts of residual water and organic solvents from the multilayer coating. Favorable burn-in The process involves heating the coated substrate at a temperature of about 150 to about 300 degrees Fahrenheit for about 10 to about 60 minutes. Heat for a while. This baking process hardens the coating and creates a hard, durable film. Become Lumu.

The compositions of the invention do not necessarily require the addition of special rheology modifiers from outside. It can be used to form coatings without Alternatively, the compositions of the invention may be It can be used as a rheology modifier by adding small amounts to coating compositions containing essential polymers. It can be made to work.

The most important criterion when evaluating the quality of the metallic effect in the coating is ( 1) Brightness when the coating is viewed at a 90° angle to the plane of its surface; (2) Oblique (3) the uniformity of the metallic effect (i.e. (no spots). Characteristics (1) and (2) are measured by goniometric photometry. Can be determined.

A method using a meter has been developed by BASF.

The instrument has a fixed incident light angle of 45". The reflected intensity detector has a specular reflection angle of 45". It can vary from 20" to 70" degrees. Is the metallic effect a specular reflection? It was found that the greater the decrease in reflection intensity at low angles, the better. observation A relationship was obtained that sufficiently discriminates the metallic effects of standard panels. this relationship is the equation % expression % (where L* indicates the intensity of light in the color space at the measurement angle) Ru.

This measurement is quantitative and reproducible. The degree of metallic effect in the example is shown. Use this measurement to

Example 1 Aqueous anionic acrylic dispersion 424.0 g of ethylene glycol monobutyl ether, deionized, in the reaction flask. 68.0 g of water, 150.0 g of styrene, 295.0 g of methyl methacrylate , 2-ethylhexyl acrylate 295.0g, hydroxyethyl acrylate 2 00.0g (1,724 equivalents), acrylic acid 60.0g (0,833 equivalents) and t-butyl peroxy-2-ethylhexanoate 12. Mixture of Og 200 g was added to produce an acrylic resin. The contents of the flask were heated to reflux (1 00℃). After refluxing for 30 minutes, the remainder of the monomer mixture was added over 2 hours. . 27.7 g of ethylene glycol monobutyl ether and peroxy-2-ether t-Butyl tylhexanoate 7,0g was added and the batch was brought to reflux (109°C). It was held for 2 hours. The batch was cooled to 70°C and N-ethylmorpholine 47.9% g (0,416 equivalents) and 89.0 g of deionized water were added. After mixing, remove 1595.0 g of ionized water was added over about 30 minutes. Viscosity is 〉Z5, weight non-volatile Component (NV) -31,5, acid per Oyohi non-volatile component! (AN/NV)-4 It was 7.6 gKOH/gNV.

This prepared acrylic dispersion was then added to the weight per epoxy (WPE) −1 70-205 diglycidyl ether of brobylene oxide (DER736, DA Add 39.2 g of U-chemical) and 624.7 g of deionized water, and the mixture Post-crosslinking was achieved by heating to 0°C. Maintain this temperature for 11 hours, then According to AN/NV-37,2, the epoxy/acid reaction was 80% complete of the theoretical value. I found out that it was completed. The NV was 26.7 and the viscosity was >z5.

Example 2 Aqueous anionic acrylic dispersion Add 51 lb of ethylene glycol monobutyl ether and deionized water to the reaction flask. 8.341b, and styrene 121b, 2-ethylhexyl methacrylate 24 1b, hydroxyethyl acrylate 241b, acrylic acid 8.71.1b (54 , 83 ii), butyl acetate 51 lb and peroxy-2-ethylhexane A mixture 241b of t-butyl acid 2.141b was added to produce an acrylic resin.

The contents of the flask were heated to reflux (104°C). After refluxing for 30 minutes, remove the The remainder of the nomer mixture was added over 2 hours. Ethylene glycol monobutyl ether 3.351b and t-butyl peroxy-2-ethylhexanoate 1.05 1b was added and the batch was held at reflux (]110°C for 2 hours. The batch was Chilled to 97℃! -111, N-ethylmorpholine 5.891b and deionized water 1 11b was added. After mixing, deionized water 1681b was added over approximately 20 minutes. . The produced acrylic dispersion was then post-crosslinked. Bisphenol A di Glycidyl ether (Epi-Rez510, Rhône Poulet, Performa Resin & Coach Inges’ J Industry 1) 4. 811b (13,30 equivalents) and the temperature was held at about 88° C. for 7 hours until the reaction was 83% of theory complete.

1251b deionized water was added to give a final NV of 25.36.

A N / N V Ha 44, 7 Te was there.

Example 3 Aqueous anionic acrylic dispersion 423.5 g of ethylene glycol monobutyl ether in the reaction flask 1 deionized 69.5g of water, 109.1g of styrene, 425.6g of butyl methacrylate , 2-ethylhexyl methacrylate 197.5g, hydroxyethyl acrylate 197.4g, acrylic acid 72.6g and peroxy-2-ethylhexanoic acid 200 g of a mixture of 17.9 g of t-butyl was added to produce an acrylic resin. Hula The contents of the Sco were heated to reflux (102°C). After refluxing for 30 minutes, the monomer -The rest of the mixture was added over 2 hours. The batch was held under reflux for 0.5 hours. Ta. 27.9 g of ethylene glycol monobutyl ether and peroxy-2- 8.8 g of t-butyl ethylhexanoate was added and the batch was heated under reflux (108°C). It was held for 2 hours. The batch was cooled to 83° C. and N-ethylmorpholine 49. 1 g and 89.8 g of deionized water were added. After mixing, add 1395 ml of deionized water. 0 g was added over approximately 20 minutes. Next, the produced acrylic dispersion was treated with Ep Add 55.1 g (0,336 equivalents) of i-Rez510 (above) and reduce the mixture to 8 Post-crosslinking was achieved by heating to 0°C. After holding the temperature for 1.5 hours, Since the measured A N/N V was 46.2, the epoxy/acid reaction was theoretical. It turned out that 40% of the value was completed. Add deionized water to final NV of 25.7 Adjusted.

Example 4 Aqueous anionic acrylic dispersion This resin was prepared according to the formulation and method of Example 3, but the reaction was continued for an additional 4.5 hours. The crosslinking reaction was completed to 70% of the theoretical value. deionized water was added to adjust the final NV to 27.6. AN/NV was 41.0.

Example 5 Aqueous anionic acrylic dispersion 423.5 g of ethylene glycol monobutyl ether, deionized, in the reaction flask. 69.5g of water, 109.1g of styrene, 425.6g of butyl methacrylate , 2-ethylhexyl methacrylate 197.5g, hydroxyethyl acrylate 197.4 g, acrylic acid 72.6 g (1,007 equivalents) and peroxy- Add 200 g of a mixture of 17.8 g of t-butyl 2-ethylhexanoate, and produced resin. The contents of the flask were heated to reflux (102°C). 30 minutes After refluxing, the remainder of the monomer mixture was added over 2 hours. Reflux this batch It was held at the bottom for 0.5 hour. 27.9g of ethylene glycol monobutyl ether and 8.8 g of t-butyl peroxy-2-ethylhexanoate were added to the batch. was kept under reflux (108°C) for 2 hours. Cool the batch to 83°C and 49.1 g of tilmorpholine and 89.8 g of deionized water were added. After mixing, 1395.0 g of deionized water was added over approximately 20 minutes. Next, this manufactured a The krylic dispersion was mixed with 70.1 g of Epi-Rez510 (above) (0,427 equivalents). ) and heating the mixture to 80° C. for post-crosslinking. The temperature is about 80 After holding at ℃ for 1.5 hours, the measured AN/NV was 44.6, so The epoxy/acid reaction was found to be 36% complete of theory. Add deionized water The final NV was adjusted to 26.1.

Example 6 Aqueous anionic acrylic dispersion This resin was prepared according to the formulation and method of Example 5, but the reaction was continued for an additional 4.5 hours. The crosslinking reaction was completed to 75% of the theoretical value. deionized water was added to adjust the final NV to 29.9. AN/NV was 35.9.

Example 7 Aqueous anionic acrylic dispersion Examples of non-crosslinked materials for comparison Add 51 lb of ethylene glycol monobutyl ether and deionized water to the reaction flask. 81b, and styrene 131 lb.

2-ethylhexyl methacrylate 241 lb, hydroxyethyl acrylate 2 41b, acrylic acid 7.31b, butyl acrylate 521b, peroxy-2- Add mixture 241b of t-butyl ethylhexanoate 2.151b and add acrylic resin. produced fat. The contents of the flask were heated to reflux (102°C). 30 minutes return Once allowed to flow, the remainder of the monomer mixture was added over a 2 hour period. This batch was heated under reflux. The temperature was maintained for 0.5 hours. Ethylene glycol monobutyl ether 3.41b and and 1.071b of t-butyl peroxy-2-ethylhexanoate. The mixture was kept under reflux (108°C) for 2 hours. The batch was cooled to 99°C and N- Ethylmorpholine 5.941b and deionized water 111b were added. after mixing , 193 lb of deionized water was added over approximately 15 minutes. Final NV is 30.5% , AN/NV was 46.7.

Example 8 Aqueous anionic polyurethane dispersion Prepared according to Polyurethane Example 1 of U.S. Pat. No. 4,791.168.

The polyester polyol resin is placed in a reaction vessel (a flask equipped with a fractionator). Talic acid 551.9g (15.8% of polyester resin), Empol 1010 (Dimer fatty acid, Emery Group, Henkel Corporation) 1923 g (54.9%), and 1,6-hexanediol 1025.1 g (29 , 3%) and 100 g of toluene. fill the trap Additional toluene may be added to improve the temperature. This mixture is heated in a nitrogen atmosphere, Water of condensation was removed. During this heating, 235.7 g of water was distilled off. Acid value is 8 or more Heating continued at approximately 200° C. until the temperature reached 200°C. Then, residual toluene is removed in vacuo. It was removed at 220°C to produce a polyester resin for use in polyurethane resin.

697.9 g of the polyester resin synthesized above, 43 g of dimethylolpropionic acid. 0g, neopentyl glycol 16. ．． 1g, isophorone diisocyanate 23 4.0g and 300g of methyl isobutyl ketone were placed in a reactor, and the isocyanate The mixture was heated under reflux (approximately 128°C) until the value became constant. Then add trimethyl to the reactor. 36.8 g of alcohol propane were added and the batch was refluxed for an additional hour. At this time At that point, the nitrogen purge was stopped and the batch was cooled to 95°C. dimethylethanolamine Added 28.6g and 1001b of water and rinsed with some of the water. Then this bag After leaving the mixture until it becomes homogeneous (about 5 minutes), add 2048.7 ml of water while stirring vigorously. g was added over 20 minutes.

After the addition is complete, the mixture is distilled at high heat with vigorous stirring to remove the water and methyl Isobutyl ketone was removed.

Water is then returned to the batch and approximately 300 g of distilled methyl isobutyl ketone is discarded. did. 238 g of n-butanol was added and the batch was held at 80° C. for 30 minutes. . This batch was filtered through a 10 micron filter and the base coat of the present invention was applied. A polyester-urethane resin used in the composition was obtained. The resulting dispersion contains solids. The content was 30% and the Gardner viscosity was 22.

Example 9 Aqueous anionic acrylic dispersion Add 424 g of ethylene glycol monobutyl ether and deionized water to the reaction flask. 68g1 and styrene 106.7g, butyl acrylate 415.7g, meth 2-ethylhexyl lylate 192.7g, hydroxyethyl acrylate 192. 7 g, 93.3 g (1,295 equivalents) of acrylic acid and peroxy-2-ethyl t-Butyl hexanoate 17. Add 200g of Og mixture to produce acrylic resin. did. The contents of the flask were heated to reflux (102°C). Refluxed for 30 minutes Afterwards, the remainder of the monomer mixture was added over a period of 2 hours. This batch was heated under reflux to 0,5 Holds time. 30g ethylene glycol monobutyl ether and peroxy t-Butyl-2-ethylhexanoate8. Og was added and the batch was heated under reflux (10 8°C) for 2 hours. The batch was cooled to 90°C and N-ethylmorpholine 74.4 g and 31.4 g of deionized water were added. After mixing, add 20 ml of deionized water 03.8g was added over approximately 20 minutes. Next, this produced acrylic dispersion was , Epi-Rez510 (above) 106. Add sg (0,651 equivalent) and mix. Post-crosslinking was achieved by heating the compound to 85°C. Keep the temperature at about 85℃ for 8 hours. After holding, the measured AN/NV was 38.5, indicating that the epoxy/acid reaction It was found that 76% of the theoretical value was completed. The final NV was 30.0%.

Example 10 Aqueous anionic acrylic dispersion In the reaction flask, add 424 g of ethylene glycol monobutyl ether and 7 g of deionized water. 0g1 and styrene 109g1 butyl acrylate 419g, methacrylic acid 2- ethylhexyl 192.8g, hydroxyethyl acrylate 192.8g, acrylate 73 g (1,013 equivalents) of lylic acid, polyethylene glycol methacrylate (silicon) Bomber HEM-20, Rhône Poulet) 20g and peroxy-2-ethyl Add 200g of a mixture of 18.8g of t-butyl hexanoate to produce acrylic resin. did. The contents of the flask were heated to reflux (100°C). Refluxed for 30 minutes Afterwards, the remainder of the monomer mixture was added over a period of 2 hours.

The batch was held under reflux for 0.5 hour. Ethylene glycol monobutyl ether 30 g of ester and t-butyl peroxy-2-ethylhexanoate 8. Add Og , the batch was held under reflux (105° C.) for 2 hours. Bring this batch to about 90℃ Cooled and added 85.8 g of N-ethylmorpholine and 26.1 g of deionized water. . After mixing, 2143.6 g of deionized water was added over approximately 20 minutes. Then, This produced acrylic dispersion was mixed into 101.9 g of Epi-Rez510 (above). (0,621 eq.) and heating the mixture to 85°C. Ta. After holding the temperature at approximately 85°C for 8 hours, the measured AN/NV was 27.5. It was found that the epoxy/acid reaction was completed to 75% of the theoretical value. Final NV was 27.6%.

Base coat manufacturing Examples 11-17: In these examples, aqueous anionic acrylic components of the present invention The dispersion was used as the main resin without the addition of rheology modifiers.

Example 11 36.14 g of the aqueous dispersion obtained in Example 1 was added with 3.3 g of deionized water with gentle stirring. Further dilution was made by adding 5.49g. pH is N-ethylmorpholine 0, sog was added and adjusted to 8.0-8.3. Aminobu with gentle stirring. Rust resin (Cymel 327, American Cyanamid, Uniin, NJ)2. Added 69g. Aluminum slurry is aluminum pigment (silver line) 5S-5251AR, 6296NV) 3.89g, ethylene glycol monobutylene 3.35 g of ether and 2-hexyloxyethyl phosphate solution (Mo - Commercially available as phosphate ester VC3419 from Bill Chemical Company) ( Prepared by mixing ethylene glycol (15% in monobutyl ether) did. The base coat can be further improved by adding 17.00 g of deionized water. diluted to a coating viscosity.

Examples 12-17 Material (WNV) NV ratio 12 13 14 15 16 17 Mix the following materials. matched = 1 Example 2 (2546) + 14.07 554.8 Example 3 (25,86 ) + 14.07 548.3 Example 5 (26,08) + 14.07 539.4 Example 4 (27,63) l 14.07 509.2 Example 6 ( 29,92) 114.07 470.2 Example 7 (30,5) 1 481 ．． 4 Deionized water 1 131 126 120 120 120 12ON-E Tilmorpholine 4.7 6.0 6.0 2.1 2.0 5.13 Below Pre-mixed the ingredients and added: Alcoa 7575 Aluminum Flake (64,0) 13.50 54.7 5 4.7 54.7 54.7 54.7 54.72-\xyloxyethyl acid ester solution (15% in ethylene glycol monobutyl ether) +0.0 2 1.5 1.5 1.5 1.5 1.5 1.5 ethylene glycol Monobutyl ether 54.7 54.7 54.7 54.7 54.7 5 4.7 Cymel (American Cyanamide) (80,0) +3.50 43. 8 43.8 43.8 43.8 43.8 43.8 Base coat on panel It was sprayed to a thickness of 0.5 to 0.7 mil. These panels are rated at 120°F Dry for 3 minutes in a forced air oven set to and baked at 250@F for 30 minutes. Metallic effect of these panels was determined.

Diluted with deionized water to the following spray viscosity as measured in a Fisher non-2 cup. .

Viscosity 141" 4 do 38" 39" 41" 39"WNV + 17.6 22.223.820.12B, 522.8pH18,088,04g, 177 ．． 1157497.81 Spray the base coat on the panel to a thickness of 0.5 mil. I got it. These panels were dried for 3 minutes in a forced air oven set at 120″F. These panels were then coated with a clear coat and baked for 30 minutes at 250”F. Ta.

The metallic effect of these panels was determined.

C value, angle photometer 165 180 195 195 165 ** Interrupt Poor appearance due to Examples 18-20: In these examples, other primary resins were used and the aqueous anionic acrylic of the present invention was used. The dispersion was used as a rheology modifier.

aluminum slurini aluminum pigment (Silver Line 5S-5251AR) (62% NY) 422.0 Ethylene Glycol monobutyl ether 358.82-hexyloxyethyl phosphate Ester solution (ethylene glycol 15% in monobutyl ether) (15% NY) 78.5 components (ItNV) 1 8 19 20 Aluminum slurry 111.6 111.8 111.6 Cymel 327 13g, 8 Li6.6 66.6 (American cyanamide, Uniin, NJ) Mixed and added the following ingredients: Example 8 (26.2%) 305.4 305.4 305.4 Example 9 ( 27.0%) 133.6 200.2 Example 10 (27.6%) 21 7.2 The following ingredients were mixed and added: N-Ethylmorpholine (ml) 2.05 3. L 1.3 deionized water 12g , 3 122.5 Li2.1 pH 7,817,817,98 Viscosity atmosphere 2 Fischer 31" 34" 33" Theoretical %N V 31 30 2 9 The panels were sprayed to a dry base coat thickness of 0.5 to 0.7 mils. this The panels were dried in a forced air oven set at 120″F for 3 minutes and then cooled. Recoat coated and baked for 30 minutes at 250°F. Then of these panels The metallic effect was determined.

C value, goniometric photometer 165 185 172 Examples 21 to 24 In these examples, other primary resins were used and the dispersions of the present invention were tested in two rheological applications. It was used as one of the gee adjusters.

aluminum slurry (Silver Line 5S-5251AR) (62% NV) 422.0 ethylene Glycol monobutyl ether 358.82-hexyloxyethyl phosphate Ester solution (ethylene glycol 15% in monobutyl ether) (15% NY) 78.5 Slurry 111.6 111.6 111.6 111.8 Cymel 327 (90%) 72.6 83.6 80.2 72.6 The following ingredients were mixed and added: Thickener 272.2 90.8 1g 1.4272.2 Mix and add the following ingredients did: Example 8 (28.2%) 204.6 271.8 238.2 357.2 Example 9 (27,0%) 133.6 133.6 133.6 - The following materials Mixed and added ingredients: N-ethylmorpholine (ml) 5.0 3.1 4.1 2.0 Deionized water LH, 9157, 91 88,4193,4pH7,847,887,817,87viscosity2Fisher -44" 41" 38" 4o" Theoretical %NV 28 29 28 27 The panels were sprayed to a dry base coat thickness of 0.5-0.7 mil. this The panels were dried in a forced air oven set at 120'F for 3 minutes and then cooled. Recoat coated and baked at 250'F for 30 minutes. Then of these panels The metallic effect was determined.

C value, goniometric photometer 180 172 180 172 Thickener: Hydrophobic fume Doshiri force, Aerosil R972 (Degussa) with suitable grinding resin and melamine The paste was sand milled in a water/organic solvent mixture. This paste is tree i9 ．． 72%, melamine 5.36% and silica 11.02%.

Summary book The present invention a) selected from the group consisting of carboxylic acid groups, carboxylic anhydride groups or mixtures thereof; Dispersing an acrylic resin with a functional group in water in the presence of a tertiary amine and, and b) The carboxylic acid group of the acrylic resin has at least two oxirane groups. an aqueous anionic acrylic dispersion produced by reacting with organic compound; Basecoats and rheology modifiers containing aqueous anionic acrylic dispersions; The present invention relates to a method of coating a material with the dispersion, and a coated substrate.

international search report j0 city 9f+・+m+a+＾-@ll+l116+Ne, p(τUEQF,’n *x-,-.

Claim 2, drawn teI a coated 5ubstrat e classified in C1ass428, subClm@s 5 Nono.

The c↓ai+as of these two groups are directed to differentinventions vMch are not eIo 1 inked as to for+e mi ngle generalinventive concept, The 1n ventions are not linked in operation sand performance completely different Ermti play.

Claims (20)

[Claims] 1. A method for producing an aqueous anionic acrylic dispersion, the method comprising: a) selected from the group consisting of carboxylic acid groups, carboxylic anhydride groups and mixtures thereof; Dispersing an acrylic resin with a functional group in water in the presence of a tertiary amine and, and b) The carboxylic acid group of the acrylic resin has at least two oxirane groups. A method characterized by reacting with organic compounds. 2. A method for producing an aqueous anionic acrylic dispersion, the method comprising: a) i) ethylenically unsaturated carboxylic acid or anhydride or mixtures thereof from about 1 to Approximately 30% by weight, ii) about 20 to about 90% by weight of other ethylenically unsaturated monomers, and iii) Ethylene with crosslinkable functional groups after formation of the post-scaled acrylic dispersion About 0 to 50% by weight of unsaturated monomer consisting of carboxylic acid groups, carboxylic anhydride groups, or mixtures thereof. forming an acrylic resin having a functional group selected from the group; dispersing in water in the presence of a tertiary amine; and b) dispersing the acrylic resin in water. reacting an oxirane group with an organic compound having at least two oxirane groups. How to characterize it. 3. An aqueous anionic acrylic dispersion prepared by the method of claim 1. 4. An aqueous anionic acrylic dispersion prepared by the method of claim 2. 5. Ethylenically unsaturated carboxylic acid or carboxylic acid anhydride (i) is acrylic acid , methacrylic acid, acryloxypropionic acid, polyacrylic acid mixture, methacrylic acid Rilic acid dimer, polymethacrylic acid mixture, crotonic acid, fumaric acid, maleic acid, Itaconic acid, maleic acid, fumaric acid, monoalkyl ester of itaconic acid, anhydrous selected from the group consisting of maleic acid, itaconic anhydride and mixtures thereof; The dispersion according to claim 4, characterized in that: 6. The ethylenically unsaturated monomer (iii) is hydroxyethyl acrylate. , hydroxyethyl methacrylate, hydroxypropyl acrylate, methacrylate Hydroxypropyl methacrylate, ethyl isocyanate methacrylate, hydroacrylic acid xybutyl, hydroxybutyl methacrylate, meta-isoprobenyl dimethyl base polyisocyanate, allyl alcohol, polypropylene glycol monoaryl ether, 2,3-dihydroxypropyl methacrylate, mono(meth)acrylate polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate and mixtures thereof. The dispersion described in . 7. The acrylic resin has an acid value of 1 to 230 mgKOH/g, The dispersion according to claim 3. 8. The weight average molecular weight of the acrylic resin is 4,000 to about 40,000. Dispersion according to claim 3, characterized in that: 9. The acrylic resin has a theoretical Tg of -30°C to about 150°C, The dispersion according to claim 3. 10. The organic compound having at least two oxirane groups is cidyl ether, diglycidyl ether of bisphenol, triglycidyl ether of triol From lycidyl ether, derivatives of cyclohexene oxide and mixtures thereof Dispersion according to claim 3, characterized in that it is selected from the group consisting of: 11. The organic compound having at least two oxirane groups is 1,4-butanedi All, neopentyl glycol/diethylene glycol, polyethylene glyco alcohol, propylene glycol, sorbitol, cresol, ethylene glycol , polypropylene glycol, 2,2,4-trimethyl-1,3-bentanedio alcohol, 1,6-hexanediol, cyclohexanedimethanol, bisphenol or resorcinol diglycidyl ether, trimethylolethane, tri- triglycidyl ether of methylolproban or glycerin, two or more consisting of cyclohexene oxide derivatives having xylan groups and mixtures thereof. Dispersion according to claim 3, characterized in that it is selected from the group consisting of: 12. The organic compound having at least two oxirane groups is oligomeric or heavy. Dispersion according to claim 3, characterized in that it is a coalescent. 13. The molar ratio between carboxylic acid groups and oxirane groups is from about 20:1 to about 1:1. The dispersion according to claim 3, characterized in that: 14. The reaction between the carboxylic acid group and the oxirane group is about 30% of theoretical completion to about Dispersion according to claim 3, characterized in that it is 100%. 15. A claim characterized in that the final acid value is from about 0 to about 225 mgKOH/g. The dispersion liquid according to item 3. 16. A) a) Consisting of carboxylic acid groups, carboxylic anhydride groups and mixtures thereof An acrylic resin having a functional group selected from the group is separated into water in the presence of a tertiary amine. scattering, and b) The carboxylic acid group of the acrylic resin has at least two oxirane groups. Aqueous anionic acrylic dispersion produced by reacting with organic compound, B ) Acrylic, polyester, alkyd, epoxy, aminoplast resin/block Crosslinking agent selected from the group consisting of polyisocyanates and mixtures thereof ,and C) Pigments, organic solvents, other crosslinkable resins, catalysts, wetting agents, modifiers, thickeners, rheolo additives, UV light stabilizers, plasticizers, antioxidants, fungicides, and their an additive selected from the group consisting of a mixture; A base coat comprising a mixture of. 17. A method for producing a base coat, comprising: a) a carboxylic acid group, a carboxylic anhydride group; and mixtures thereof. b) dispersing the acrylic resin in water in the presence of a tertiary amine; An aqueous anionic compound is produced by reacting with an organic compound having at least two oxirane groups. forming a krill dispersion; C) Acrylic, polyester, alkyd, epoxy, aminoplast resin/bro crosslinked polyisocyanates selected from the group consisting of coated polyisocyanates and mixtures thereof; Add the agent, d) Pigments, organic solvents, other crosslinkable resins, catalysts, wetting agents, modifiers, thickeners, rheolo additives, UV light stabilizers, plasticizers, antioxidants, fungicides, and their A method characterized in that adding an additive selected from the group consisting of a mixture. 18. A rheology modifier comprising the dispersion according to claim 4. 19. 17. A method of coating a substrate with a multilayer coating, comprising: a base coat according to claim 16; Apply on the substrate and then apply at least one clear coat on top of this base coat. A method characterized by: 20. A substrate coated with at least the basecoat of claim 16.